CN101861288B - Aluminum titanate based ceramic honeycomb structure, process for production of the same and raw material powder for the production thereof - Google Patents
Aluminum titanate based ceramic honeycomb structure, process for production of the same and raw material powder for the production thereof Download PDFInfo
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- CN101861288B CN101861288B CN2008801162970A CN200880116297A CN101861288B CN 101861288 B CN101861288 B CN 101861288B CN 2008801162970 A CN2008801162970 A CN 2008801162970A CN 200880116297 A CN200880116297 A CN 200880116297A CN 101861288 B CN101861288 B CN 101861288B
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- glassy phase
- titanate
- aluminum
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- 229910000505 Al2TiO5 Inorganic materials 0.000 title claims abstract description 49
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
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- C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/478—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on aluminium titanates
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Abstract
An aluminum titanate based ceramic honeycomb structure provided with many flow paths separated by porous partition walls, characterized in that the partition walls comprise at least both an aluminum titanate main crystal phase containing solid-soluted MgO and SiO2 and a glass phase, that the glass phase comprises 40 to 80mass% of SiO2 and 1 to 20mass% of MgO, that the mean size of the glass phase in the section of the partition walls is 30[mu]m or below, and that the area fraction of the glass phase in the section of the partition walls is 2 to 12% based on the total area of the aluminum titanate main crystal phase and the glass phase; and a process for the production of the honeycomb structure.
Description
Technical field
The present invention relates to aluminum-titanate-based ceramic honeycomb structure, its manufacture method and for the manufacture of its material powder.Aluminum-titanate-based ceramic honeycomb structure, its manufacture method of wherein relating to the ceramic honeycomb filter that uses in the waste gas that comprises PM that is preferred for purifying by discharges such as Diesel engines reach the material powder for the manufacture of it.
Background technology
Include in the waste gas of Diesel engine take the coal that is formed by carbonaceous and the SOF composition that is become to be grouped into by high boiling hydrocarbon (Soluble Organic Fraction: the solubility organic principle) as PM (the Particulate Matter: particulate matter) of principal component, when it is discharged in atmosphere, has to human body and environment and bring dysgenic danger.Therefore, in the past, the ceramic honeycomb filter that is used for capturing PM (following with ceramic honeycomb filter referred to as " honeycomb filter ") was installed in the middle of the blast pipe of Diesel engine.With capture, the honeycomb filter of PM in purifying exhaust air one be illustrated in Fig. 1 (a) and Fig. 1 (b).Honeycomb filter 10 is comprised of ceramic honeycomb structure (following sometimes also referred to as honeycomb molded body) and the upstream side seal 6a of section, the downstream side seal 6c of section, described ceramic honeycomb structure is comprised of the porous partition 2 that forms a plurality of outflow sides seal path 3 and inflow side seal path 4 and periphery wall 1, and the described upstream side seal 6a of section and the downstream side seal 6c of section flow into side end face 8 and waste gas with the waste gas of outflow side seal path 3 and inflow side seal path 4 and flow out side end face 9 and alternately be sealed to tartan.
For this honeycomb filter, require it in use to capture the contained particulate of waste gas with high efficiency, reduce the pressure loss and reduce the load that engine is applied, but work as the particulate that captures when becoming many, because thereby the pore of partition stops up pressure loss increase, therefore need burning to remove the particulate that captures and make honeycomb filter regeneration.Therefore like this, in the high temperature when repeatedly being exposed to combustion particle due to honeycomb filter, require high-fire resistance and high resistance to sudden heating, the material as in the past formation porous partition generally uses cordierite (5SiO
22AlO
22MgO) or carborundum (SiC).
In the situation that use cordierite to consist of partition, because thermal coefficient of expansion is low, be 10 * 10
-7Therefore/℃ left and right is difficult to produce the be full of cracks that causes because of thermal shock, and thermal shock resistance is excellent, but when burning under accumulation has the state of a large amount of particulates, thus sometimes the temperature of honeycomb filter rise so high partition can the molten damage of part.Therefore, excessively rise in order not make ignition temperature, need to carry out strict control, exist the manufacturing cost of waste gas purification apparatus or running expense to increase such problem.
In the situation that use carborundum to consist of partition, although excellent heat resistance because thermal coefficient of expansion is large, is 40 * 10
-7/ ℃, therefore sometimes produce the be full of cracks breakage because of the thermal shock stress honeycomb molded body.In order to relax thermal stress, have the honeycomb molded body that will be divided into to be pasted together the method for doing as a whole use, but have its effect not fully, because of the problem of cutting apart and the rising of stickup cost is such.
In order to address the above problem, motion recently has use aluminium titanates (Al
2TiO
5) as the material that consists of honeycomb molded body.Aluminium titanates has heat resistance and the little and excellent heat resistance impact of thermal coefficient of expansion over 1700 ℃.But, have such problem: the little thermal coefficient of expansion of aluminium titanates is to cause due to microscopic checks that the thermal coefficient of expansion anisotropy that exists because of the aluminium titanates crystallization produces in sintering process, on the other hand, due to the existence of this microscopic checks, there is the such problem of mechanical strength decline of honeycomb molded body.That is, there be the little coefficient of expansion such problem opposite to high strength in existing aluminium titanates.In addition, because existing aluminium titanates has the decomposition region the temperature range of 800～1280 ℃ usually, therefore also there is following problem: can not use steadily in the long term under such temperature range.In order to solve the problem of so existing aluminium titanates, disclose following technology.
Disclose a kind of aluminum magnesium titanate crystalline texture thing and manufacture method thereof in WO05/105704, described aluminum magnesium titanate crystalline texture thing is by at composition formula Mg
xAl
2 (1-x)Ti
(1+x)O
5The part of the Al atom of the superficial layer at least of the aluminum magnesium titanate crystallization of (in formula, 0.1≤x＜1) expression is formed by the solid solution that the Si atom replaces, and has-6 * 10
-6～6 * 10
-6Thermal coefficient of expansion (1/K), and the surplus ratio of the aluminum magnesium titanate when keeping 300 hours in the atmosphere of 1100 ℃ is more than 50%, wherein, record: described works has the intrinsic heat resistance of aluminium titanates and minimum thermal coefficient of expansion, resistance to sudden heating is excellent, has simultaneously high pyrolytic and large mechanical strength.Yet, begun in recent years the more high performance honeycomb filter of requirement, in No. WO05/105704, the honeycomb filter of record considers it is inadequate from taking into account the such viewpoint of low thermal coefficient of expansion and high strength, particularly with regard to its pressure loss characteristic, does not reach gratifying degree.Thereby, in No. WO05/105704 in the method for record, be difficult to obtain resistance to sudden heating, intensity, stability at high temperature, pressure loss performance are brought up to simultaneously the honeycomb filter of practical no problem level.
Disclose a kind of ceramic body and manufacture method thereof in WO06/39255, described ceramic body has the aluminium titanates crystalline phase of 50～95 quality % and the glassy phase of 5～50 quality %, and described glassy phase has by 50～90% SiO
2, 1～25% Al
2O
3, 0.5～10% TiO
2, 0.5～20% R
2O (R is the element that selects in the group that free Li, Na, K, Ru, Cs and Fr consist of), and the composition that consists of of 0.5～20% R ' O (R ' for selecting the element in the group that free Be, Mg, Ca, Ba and Ra consist of), wherein, record the ceramic body that resistance to impact and heat-resisting cyclicity excellence can be provided, be suitable for high-temperature use.Yet, begun in recent years the more high performance honeycomb filter of requirement, the honeycomb filter of putting down in writing in WO06/39255 considers it is inadequate from taking into account the such viewpoint of low thermal coefficient of expansion and high strength, particularly with regard to the heat endurance of its pressure loss characteristic and 800～1250 ℃, do not reach gratifying degree.Thereby the method for putting down in writing in WO06/39255 is difficult to obtain the stability under resistance to sudden heating, intensity, high temperature, pressure loss performance are brought up to the practical honeycomb filter of no problem level simultaneously.In addition, be not documented in detail about manufacture method, use but need to pulverize at the glass of the special composition of 1600 ℃ of lower meltings as raw material as can be known from embodiment, therefore have the high such problem of manufacturing cost yet.
Disclose a kind of alumina titanate ceramics and manufacture method thereof in (Japan) Unexamined Patent 5-85818, the crystalline phase of described alumina titanate ceramics constitute aluminium titanates 60～85%, rutile 10～25%, corundum 2～10%, and mullite 2～10%, glassy phase is below 5%, wherein, record: the aluminium titanates that thermal cycle excellent in te pins of durability and embedding casting property excellence can be provided.Yet therefore the alumina titanate ceramics of putting down in writing in (Japan) Unexamined Patent 5-85818 exists owing to containing in a large number rutile 10～20% problem that thermal coefficient of expansion is large, poor thermal shock resistance is such.In addition, begin in recent years the more high performance honeycomb filter of requirement, with regard to the heat endurance of its pressure loss performance and 800～1250 ℃, do not reached gratifying degree.Thereby the method for putting down in writing in (Japan) Unexamined Patent 5-85818 is difficult to obtain the stability under resistance to sudden heating, intensity, high temperature, pressure loss performance are brought up to the practical honeycomb filter of no problem level simultaneously.
Disclose a kind of ceramic material that is made of the aluminium titanates of silicate in (Japan) examined patent publication 60-5544, the aluminium titanates of described silicate has the Al by 50～60 % by weight
2O
3, 40～45 % by weight TiO
2, the kaolin of 2～5 % by weight and 0.1～1 % by weight the chemical composition that forms of magnesium silicate, be that raw material below 0.6 μ m forms by granularity, wherein, record it and have high impact and mechanical strength.Yet, begun in recent years the more high performance honeycomb filter of requirement, the melikaria of putting down in writing in (Japan) examined patent publication 60-5544 considers it is inadequate from taking into account the such viewpoint of low thermal coefficient of expansion and high strength, particularly with regard to the heat endurance of its pressure loss characteristic and 800～1250 ℃, do not reach gratifying degree.Thereby the method for putting down in writing in (Japan) examined patent publication 60-5544 is difficult to obtain the stability under resistance to sudden heating, intensity, high temperature, pressure loss performance are brought up to the practical honeycomb filter of no problem level simultaneously.
(Japan) JP 2006-96634 discloses the porosity 51～75%, average pore diameter 10～40 μ m, has stipulated the aluminum titanate-based porous ceramic bodies of the distribution of pore diameter, wherein, record according to such formation, can obtain the ceramic honeycomb filter that heat resistance and resistance to sudden heating are excellent, have simultaneously intensity no problem in low pressure loss characteristic and practicality.Yet, having begun in recent years the more high performance honeycomb filter of requirement, the heat endurance of 800～1250 ℃ of the porous ceramic bodies of putting down in writing in (Japan) JP 2006-96634 does not reach gratifying degree.In addition, consider it is inadequate from taking into account the such viewpoint of low thermal coefficient of expansion and high strength, obtain the stability under resistance to sudden heating, intensity, high temperature, pressure loss performance are brought up to the practical honeycomb filter of no problem level simultaneously, need further to improve.
Summary of the invention
As mentioned above, in the aluminium titanates of prior art, consider it is inadequate from taking into account the such viewpoint of low thermal coefficient of expansion and high strength, obtain the stability under resistance to sudden heating, intensity, high temperature, pressure loss performance are brought up to the practical honeycomb filter of no problem level simultaneously, need further to improve.Thereby, the object of the invention is to, a kind of aluminum-titanate-based ceramic honeycomb structure, its manufacture method and material powder thereof are provided, and the excellent heat stability of the resistance to sudden heating of described aluminum-titanate-based ceramic honeycomb structure, pressure loss characteristic and 800～1250 ℃ has been improved intensity simultaneously.
Result in view of the wholwe-hearted research of above-mentioned purpose, the discoveries such as the inventor, the forming of glassy phase in the ceramic honeycomb structure that is consisted of by primary crystallization and the glassy phase of aluminium titanates by regulation, size and have ratio, produce a large amount of microscopic checks in calcination process, its result, the thermal coefficient of expansion of honeycomb molded body diminishes, and the intensity increase, thereby has completed the present invention.
That is, aluminum-titanate-based ceramic honeycomb structure of the present invention is characterised in that, has a plurality of paths that the partition with porous separates, and described partition has MgO and SiO by solid solution at least
2The primary crystallization of aluminium titanates and glassy phase consist of, described glassy phase contains the SiO of 40～80 quality %
2And the MgO of 1～20 quality %, the average-size of the glassy phase in the section of described partition is below 30 μ m, and the described glassy phase in the section of described partition is 2～12% with respect to the area ratio of the total area of the primary crystallization of described aluminium titanates and described glassy phase.
Another aluminum-titanate-based ceramic honeycomb structure of the present invention is characterised in that, has a plurality of paths that the partition with porous separates, and described partition has MgO and SiO by solid solution at least
2The primary crystallization of aluminium titanates and glassy phase consist of, described glassy phase contains the SiO of 40～80 quality %
2And the MgO of 1～20 quality %, the average-size of the glassy phase in the section of described partition is below 30 μ m, described glassy phase is more than 1 quality % and less than 10 quality % with respect to the mass fraction of the total of the primary crystallization of described aluminium titanates and described glassy phase.
Above-mentioned solid solution has MgO and SiO
2The primary crystallization of aluminium titanates in, the solid solution capacity of MgO is preferably 0.2～5 quality %, and SiO
2Solid solution capacity be preferably 0.1～1.5 quality %.
the porosity of above-mentioned partition is preferably 40～70%, average pore diameter is preferably 10～40 μ m, pore distribution bias σ [wherein, σ=log (D20)-log (D80), D20 is the curve of expression pore diameter and the relation of accumulating pore volume (having accumulated the value from the pore diameter of maximum to the pore volume specific pore diameter), pore diameter (μ m) when being illustrated in 20% the pore volume that is equivalent to whole pore volume, pore diameter (μ m) when D80 is illustrated in 80% the pore volume that is equivalent to whole pore volume equally.D80＜D20 wherein.] be preferably below 0.4.
The venting quality of above-mentioned partition is preferably 2 * 10
-12m
2Above.
More than the A axial compression contracting intensity of above-mentioned honeycomb molded body is preferably 4MPa.The thermal coefficient of expansion of above-mentioned partition is preferably 12 * 10
-7/ ℃ below.When above-mentioned partition was kept 100 hours in the atmosphere of 1100 ℃, the surplus ratio of aluminium titanates was preferably more than 95%.
The manufacture method of aluminum-titanate-based ceramic honeycomb structure of the present invention is characterised in that, will contain 0.05～0.5 quality %Na with respect to 100 mass parts
2The alumina powder of O with contain the 0.5 following Na of quality %
2The total amount of the powder in the titania powder of O is adjusted to take molar ratio computing as the scope of 47: 53～53: 47, at least mix the SiO 2 powder of 1～6 mass parts and the following magnesium oxide source powder of average grain diameter 5 μ m of 0.5～5 mass parts, after making the formed body of alveolate texture by this material that mixes, average speed with 10～100 ℃/hr heats up in the temperature range of 1300 ℃ to 1350 ℃ again, and calcine at the highest maintenance temperature of 1400～1650 ℃, obtain thus by solid solution, MgO and SiO being arranged at least
2The primary crystallization of aluminium titanates and the aluminum-titanate-based ceramic honeycomb structure that consists of of glassy phase.
The average grain diameter of above-mentioned alumina powder is preferably 0.1～10 μ m, and the average grain diameter of above-mentioned titania powder is preferably 0.05～3 μ m, and the average grain diameter of above-mentioned SiO 2 powder is preferably 0.1～30 μ m.The average grain diameter of above-mentioned alumina powder is 2～6 μ m more preferably.
Preferably add the pore-creating material in above-mentioned composite material.
Preferably keep more than 24 hours at the highest above-mentioned maintenance temperature.
Material powder for the manufacture of aluminum-titanate-based ceramic honeycomb structure of the present invention is for the manufacture of by solid solution, MgO and SiO being arranged at least
2The primary crystallization of aluminium titanates and the material powder of the aluminum-titanate-based ceramic honeycomb structure that consists of of glassy phase, it is characterized in that, be will contain 0.05～0.5 quality %Na with respect to 100 mass parts
2The alumina powder of O and contain the 0.5 following Na of quality %
2The total amount of the powder in the titania powder of O is adjusted to take molar ratio computing as 47: 53～53: 47 scopes, mix at least can 1～6 mass parts SiO 2 powder and the following magnesium oxide source powder of average grain diameter 5 μ m of 0.5～5 mass parts form.
Aluminum-titanate-based ceramic honeycomb structure of the present invention has MgO and SiO by being present in solid solution
2The primary crystallization of aluminium titanates and the composition of the glassy phase between primary crystallization and size adjustment to optimum state, therefore thereby improved simultaneously resistance to sudden heating, pressure loss characteristic and heat endurance (800～1250 ℃) and intensity, be particularly suitable for the high and external diameter of the porosity of used for diesel engine and surpass the so large-scale ceramic honeycomb filter of 200mm.
Utilize method of the present invention, can will MgO and SiO be arranged by solid solution
2The primary crystallization of aluminium titanates and the glassy phase of the aluminum-titanate-based ceramic that consists of of glassy phase control to best composition and size, can make easily aluminum-titanate-based ceramic honeycomb structure of the present invention.
The material powder of the application of the invention can be made aluminum-titanate-based ceramic honeycomb structure of the present invention easily.
Description of drawings
Fig. 1 (a) is the generalized section of an example of expression honeycomb filter on perpendicular to the direction of path.
Fig. 1 (b) is in the generalized section that is parallel to an example of expression honeycomb filter on the direction of path.
Fig. 2 (a) means the SEM photo of an example of the partition section of honeycomb molded body.
Fig. 2 (b) is the schematic diagram with the glassy phase of the partition section of slash mark honeycomb molded body.
Fig. 2 (c) calculates the figure of method of the number of the microscopic checks that the crystalline phase of honeycomb molded body produces for explanation.
Fig. 3 means the pore diameter of the partition of the honeycomb molded body of making in embodiment 3 and the curve map of the relation between pore volume.
Fig. 4 is in the generalized section that is parallel to an other example of expression honeycomb filter on the direction of path.
The specific embodiment
[1] aluminum-titanate-based ceramic honeycomb structure
(1) the 1st honeycomb molded body
For first aluminum-titanate-based ceramic honeycomb structure of the present invention (following also referred to as honeycomb molded body) of a plurality of paths that separate for the partition that has with porous, it is characterized in that, above-mentioned partition has MgO and SiO by solid solution at least
2The primary crystallization of aluminium titanates and glassy phase consist of, above-mentioned glassy phase contains the SiO of 40～80 quality %
2And the MgO of 1～20 quality %, the average-size of the glassy phase in the section of above-mentioned partition is below 30 μ m, the above-mentioned glassy phase in the section of above-mentioned partition has MgO and SiO with respect to above-mentioned solid solution
2The primary crystallization of aluminium titanates and the area ratio of the total area of above-mentioned glassy phase be 2～12%.
By solid solution MgO and SiO in the aluminium titanates primary crystallization
2, improved the heat endurance of 800～1250 ℃, and by contain the SiO of 40～80 quality % in glassy phase
2And the MgO of 1～20 quality %, combination in glassy phase between the crystallization of above-mentioned aluminium titanates, the microscopic checks that imports in the calcination process midfeather is by miniaturization, thereby when the thermal coefficient of expansion of honeycomb molded body diminished, the intensity of honeycomb molded body increased.
Glassy phase contains the SiO of 40～80 quality %
2And the MgO of 1～20 quality %.By contain the SiO of 40～80 quality % in glassy phase
2, can form as amorphous glassy phase, simultaneously by containing the MgO of 1～20 quality %, the fusing point step-down of glassy phase.Therefore in calcination process, by generate liquid phase in the temperature field by alumina raw material powder and the synthetic aluminium titanates of titanium dioxide material powder, after calcining, formation combines solid solution with fine glassy phase MgO and SiO
2The complex tissue of aluminium titanates primary crystallization.By with the primary crystallization of fine glassy phase in conjunction with above-mentioned aluminium titanates, it retrains grow, and therefore, the microscopic checks that produces because of the thermal expansion anisotropy of aluminium titanates becomes fine, and its number also increases.When the MgO quantity not sufficient 1 quality % that contains in glassy phase, reveal insufficiently due to the eutectic of glassy phase, so glassy phase exists with larger piece, when being 1 quality % when above, along with the MgO amount increases, glassy phase disperses to exist imperceptibly.Like this, more disperse in partition to form fine glassy phase, the microscopic checks that produces in the aluminium titanates crystalline phase is got over miniaturization, and the thermal coefficient of expansion of honeycomb molded body diminishes, and the intensity of honeycomb molded body increases simultaneously.On the other hand, in the situation that the MgO that contains in glassy phase amount surpasses 20 quality %, the fusing point of glassy phase is too low, and the softening temperature of honeycomb molded body descends, as the heat resistance variation of the feature of aluminum-titanate-based ceramic.
The average-size of the glassy phase in the section of partition is below 30 μ m.When above-mentioned average-size during greater than 30 μ m, because the constraint of the primary crystallization of aluminium titanates dies down, so the miniaturization of microscopic checks is suppressed, and it is large that microscopic checks becomes, and because its number also tails off, so thermal coefficient of expansion can not descend fully, and intensity is insufficient simultaneously.One example of the partition section of honeycomb molded body is shown in Fig. 2 (a) with the SEM photo.As shown in Fig. 2 (b) bend, glassy phase 2 is present in the gap of the crystalline phase 1 of aluminium titanates and crystalline phase 1, with the size of its maximum length as glassy phase 2.For the average-size of glassy phase 2, measure the size of 20 place's glassy phases 2, draw with its mean value calculation.Below the preferred 20 μ m of the average-size of glassy phase, further below preferred 10 μ m, most preferably below 5 μ m.
Above-mentioned glassy phase in the section of partition has MgO and SiO with respect to solid solution
2The primary crystallization of aluminium titanates and the area ratio of the total area of glassy phase be 2～12%.In the situation that the area ratio less than 2% of above-mentioned glassy phase, the combination of aluminium titanates crystallization dies down, and the miniaturization of microscopic checks simultaneously is insufficient, and the intensity of honeycomb molded body can not improve.In the situation that the area ratio of above-mentioned glassy phase surpasses 12%, because the impact of glass becomes large, so the intensity of honeycomb molded body diminishes, and thermal coefficient of expansion also becomes large simultaneously.The area ratio of above-mentioned glassy phase is preferably 2～8%, and more preferably 3～6%.
Glassy phase is preferably except containing the SiO of 40～80 quality %
2And beyond the MgO of 1～20 quality %, also contain the Al of 10～40 quality %
2O
3, 0.5～10 quality % TiO
2, 0.5～5 quality % Na
2The K of O, 0.5～5 quality %
2O。By being set as such composition, the glassy phase eutectic is revealed and is promoted the miniaturization of microscopic checks, takes into account low thermal coefficient of expansion and high strength.For Na
2O and K
2O by containing respectively 0.5～5 quality %, can make the fusing point of glassy phase further descend, and helps to take into account low thermal coefficient of expansion and high strength.Glassy phase further preferably contains the SiO of 50～70 quality %
2, the MgO of 2.5～10 quality %, the Al of 15～30 quality %
2O
3, 1～8 quality % TiO
2, 1～4 quality % Na
2The K of O and 1～4 quality %
2O。
In the primary crystallization of described aluminium titanates, preferred solid solution has the MgO of 0.2～5 quality % and the SiO of 0.1～1.5 quality %
2MgO and SiO by this scope of solid solution
2, improving aluminum-titanate-based ceramic in the heat endurance of 800～1250 ℃, improve the intensity of aluminium titanates crystallization itself, the intensity of honeycomb molded body is further improved.The solid solution capacity of further preferred MgO is 0.5～3 quality %, further preferred SiO
2Solid solution capacity be 0.1～0.6 quality %.
As shown in Fig. 2 (c), the number of microscopic checks 3 can utilize according to the SEM photo of partition section intersection method (calculate the number of the microscopic checks 3 that the straight line draw arbitrarily intersects, be scaled the method that the per unit length of the straight line of removing pore calculates) to try to achieve.The preferred 50/mm of number of the microscopic checks of trying to achieve with the intersection method is above, further preferred 100/more than mm.
Honeycomb molded body has MgO and SiO by solid solution in fact
2Aluminium titanates primary crystallization and comprise at least MgO and SiO
2Glassy phase consist of, in addition, action effect of the present invention the TiO that can also not include trace in influential scope
2, Al
2O
3, spinelle, mullite etc. crystallization.Their content is not particularly limited, but with respect to the total of the crystallization beyond primary crystallization and its be preferably below 10%, more preferably below 5 quality %.The content of crystalline phase is according to the X-ray diffractogram of Powdered sample, by (230) face diffracted intensity (I of aluminium titanates
AT (230)), Al
2O
3(104) face diffracted intensity (I of corundum
Corundum (104)), TiO
2(110) face diffracted intensity (I of rutile
Rutile (110)), and (311) face diffracted intensity (I of spinelle
Spinelle (311)) the calculating such as strength ratio.In addition, in the scope that does not affect action effect of the present invention, also can contain CaO, BaO, Fe
2O
3, Li
2O, SrO, Y
2O
3Deng.
(2) the 2nd honeycomb molded bodies
For second aluminum-titanate-based ceramic honeycomb structure of the present invention of a plurality of paths that separate for the partition that has with porous, above-mentioned partition has MgO and SiO by solid solution at least
2The primary crystallization of aluminium titanates and glassy phase consist of, above-mentioned glassy phase contains the SiO of 40～80 quality %
2And the MgO of 1～20 quality %, the average-size of the glassy phase in the section of above-mentioned partition is below 30 μ m, and above-mentioned glassy phase is more than 1 quality % and less than 10 quality % with respect to the mass fraction of the total area of the primary crystallization of above-mentioned aluminium titanates and above-mentioned glassy phase.
Above-mentioned partition has MgO and SiO by solid solution at least
2The primary crystallization of aluminium titanates and the SiO that glassy phase consists of, above-mentioned glassy phase contains 40～80 quality %
2And the average-size of the glassy phase in the section of the MgO of 1～20 quality %, above-mentioned partition is below 30 μ m, and these contents are identical with the 1st aluminum-titanate-based ceramic honeycomb structure, so description thereof is omitted, and the mass fraction of above-mentioned glassy phase is elaborated.
Above-mentioned glassy phase has MgO and SiO with respect to solid solution
2The primary crystallization of aluminium titanates and the mass fraction of the total of glassy phase be that 1 quality % is above and less than 10 quality %.In the situation that the mass fraction less than 1 quality % of above-mentioned glassy phase, the combination between the aluminium titanates crystallization dies down, and the miniaturization of microscopic checks simultaneously is insufficient, and the intensity of honeycomb molded body can not improve.In the situation that the mass fraction of glassy phase is more than 10 quality %, because the impact of glass becomes large, so the intensity of honeycomb molded body diminishes, and thermal coefficient of expansion also becomes large simultaneously.More than the preferred 1 quality % of the mass fraction of above-mentioned glassy phase and less than 5 quality %.
(3) loose structure
As illustrating in the problem of prior art, existing aluminium titanates is owing to being difficult to take into account low thermal coefficient of expansion and high strength, therefore, be difficult to regulate the honeycomb molded body that the porosity, pore distribution etc. obtain having the low pressure loss performance because intensity is insufficient.With respect to this, honeycomb molded body of the present invention as described above, thereby by the existence that utilizes specific glassy phase have miniaturization the crack, can keep the low heat expansion of aluminum-titanate-based ceramic and have high intensity, by the porosity or the pore distribution optimization with partition, thereby compare pressure loss excellent performance with existing honeycomb molded body.
Aluminum-titanate-based honeycomb molded body of the present invention preferably is set as the porosity 40～70%, average pore diameter is set as 10～40 μ m, average pore distribution bias σ is set as below 0.4.By being set as such structure, the honeycomb molded body that can obtain having the low pressure loss performance.At this, σ=log (D20)-log (D80), as shown in Figure 3, D20 is the curve of the relation of expression pore diameter and accumulation pore volume (having accumulated the value that draws to the pore volume specific pore diameter from the pore diameter of maximum), pore diameter (μ m) when being illustrated in 20% the pore volume that is equivalent to whole pore volume, the pore diameter (μ m) when D80 is illustrated in 80% the pore volume that is equivalent to whole pore volume equally.D80＜D20 wherein.The relation of pore diameter and accumulation pore volume can be tried to achieve with mercury penetration method.
When porosity less than 40%, sometimes can not realize sufficient low pressure loss performance, when the porosity surpasses 70%, sometimes can not obtain practical sufficient intensity.The further preferred scope of the porosity is 45%～64%.
When average pore diameter less than 10 μ m, sometimes can not realize sufficient low pressure loss performance, when average pore diameter surpasses 40 μ m, the capture hydraulic performance decline of particulate sometimes.The further preferred scope of average pore diameter is 15～30 μ m.
Aluminum-titanate-based honeycomb molded body of the present invention preferably is set as 2 * 10 with venting quality
-12m
2Above.Venting quality means the index of the aeration of porous partition, by venting quality is set as 2 * 10
-12m
2Above, as can to obtain having low pressure loss honeycomb molded body.
As mentioned above, pore distribution bias σ is logarithm poor of the logarithm of D20 and D80, is the index of the distribution of regulation pore diameter.The little expression pore diameter distribution of σ sharp-pointed (sharp).In the situation that the porosity 40～70%, average pore diameter 10～40 μ m, σ are below 0.4, help the pore of low pressure loss characteristic many, and the thick pore that makes the small pore of pressure loss variation and intensity is descended tails off, and can make and take into account low pressure loss and high-intensity honeycomb molded body.On the other hand, when pore distribution bias σ surpassed 0.4, therefore the ratio increase due to the pore that makes the pressure loss and intensity variation can not obtain low pressure loss and high-intensity honeycomb molded body.Pore distribution bias σ more preferably below 0.35, most preferably is below 0.3.
(4) shape
Consider from taking into account low pressure loss and high-intensity viewpoint, the thickness of the partition of honeycomb molded body is preferably 0.1～0.5mm, and unit interval is preferably 1～3mm.The shape perpendicular to the axial section of path of honeycomb molded body is not particularly limited, viewpoint on making is considered the arbitrary shape preferred triangle, quadrangle, hexagon and circle, consider from the viewpoint of intensity and filter area, particularly preferably tetragonal path.Preferred partition is linearly extended plane, but do not strengthen waste gas by path in the time the passage resistance scope in also can bending.
(5) characteristic
Aluminum-titanate-based ceramic honeycomb structure of the present invention utilizes solid solution that MgO and SiO are arranged
2The primary crystallization of aluminium titanates improve the heat endurance of 800～1250 ℃.And then, contain MgO and SiO by comprising
2Glassy phase, import a large amount of fine microscopic checks in partition, thermal coefficient of expansion diminishes and improves resistance to sudden heating, has simultaneously high strength.More than the A axial compression contracting intensity of honeycomb molded body particularly can be set as 4MPa.In addition, the thermal coefficient of expansion of honeycomb molded body particularly can be set as 12 * 10
-7/ ℃ below.Preferably can be set as 10 * 10
-7/ ℃ below.Thereby, in the situation that import the pore is communicated with partition, the porosity is increased to 40～70% in order to obtain the low pressure loss performance, also can obtain having the honeycomb molded body that sufficient intensity is gone up in practicality.
As previously mentioned, honeycomb molded body passes through MgO and SiO
2Be solid-solubilized in aluminium titanates, the decomposition in the time of can effectively preventing from being exposed to for a long time 800～1250 ℃ (aluminium titanates is in the decomposition of rutile and corundum), can make the surplus ratio of the aluminium titanates when keeping 100 hours in the atmosphere of 1100 ℃ is more than 95%.
(6) honeycomb filter
As shown in Fig. 1 (a) and Fig. 1 (b), outflow side seal path 3 by making honeycomb molded body and the waste gas of inflow side seal path 4 flow into side end face 8 and waste gas and flow out side end face 9 and alternately be sealed to tartan, can obtain honeycomb filter 10.Be used to form the hole sealing 6a of outflow side seal path 3 and inflow side seal path 4,6c may not be configured in the end face 8,9 of path, also can be formed at from the position of the inboard of end face inlet passage.Particularly as shown in Figure 4, when making the hole sealing 6b that is disposed at inflow side seal path 4 be configured in the path inboard, consider more preferably from the viewpoint of exhaust-gas purifying performance and micro particle catching performance.Namely, in the situation that be shown in the honeycomb molded body of Fig. 4, the honeycomb molded body that has the existing structure of hole sealing with the both ends that are shown in 1 (a) and Fig. 1 (b) is compared, owing to disperseing trap particles at the upstream side that flows into side opening sealing 6b and outflow side opening sealing 6c, therefore can capture more particulate, and because the primary crystallization of a wall material is that solid solution has stable on heating MgO and SiO
2Aluminium titanates, therefore can increase the amount of collected of molten damage boundary particulate, the combustion expense performance of Diesel engine can be significantly improved at the interval that result can prolonging combustion.The aperture area of outflow side seal path 3 and inflow side seal path 4 needn't be identical, also can be different.
[2] manufacture method
Of the present invention have MgO and SiO by solid solution at least
2The primary crystallization of aluminium titanates and the aluminum-titanate-based ceramic honeycomb structure that consists of of glassy phase can followingly make: will contain 0.05～0.5 quality %Na with respect to 100 mass parts
2The alumina powder of O with contain the 0.5 following Na of quality %
2The total amount of the powder in the titania powder of O is adjusted to take molar ratio computing as the scope of 47: 53～53: 47, at least mix the SiO 2 powder of 1～6 mass parts and the following magnesium oxide source powder of average grain diameter 5 μ m of 0.5～5 mass parts, after making the formed body of alveolate texture by this material that mixes, average speed with 10～100 ℃/hr heats up in the temperature range of 1300 ℃ to 1350 ℃ again, and calcine at the highest maintenance temperature of 1400～1650 ℃, obtain thus by solid solution, MgO and SiO being arranged at least
2The primary crystallization of aluminium titanates and the aluminum-titanate-based ceramic honeycomb structure that consists of of glassy phase.
(1) material powder
For material powder, will contain 0.05～0.5 quality %Na with respect to 100 weight portions
2The alumina powder of O with contain the 0.5 following Na of quality %
2The titania powder of O is adjusted to and is calculated in molar ratio as 47: 53～total amount of powder in the scope of 53: 47, mix at least the SiO 2 powder of 1～6 mass parts and the following magnesium oxide source powder of average grain diameter 5 μ m of 0.5～5 mass parts.
Be set as 47: 53～scope of 53: 47 by the mol ratio with above-mentioned alumina powder and above-mentioned titania powder, can reduce remaining titanium dioxide and aluminium oxide when calcining synthetic aluminium titanates, and the heat resistance that the performance aluminium titanates has originally.The mol ratio of titania powder and alumina powder is preferably 48: 52～and 52: 48.
The average grain diameter of alumina powder is preferably 0.2～10 μ m.When above-mentioned average grain diameter less than 0.2 μ m, promote densified, the pore of aluminum-titanate-based ceramic to tail off.Therefore, for obtain having the required porosity, the porous body of average pore diameter, pore distribution bias and venting quality, need to add the pore-creating materials in a large number, and the low pressure loss performance is insufficient sometimes.When above-mentioned average grain diameter surpassed 10 μ m, therefore the aluminium oxide that the delayed heat coefficient of expansion is large due to the synthetic insufficient of aluminium titanates can not obtain low thermal coefficient of expansion.The average grain diameter of alumina powder is 2～8 μ m more preferably.At present when making aluminium titanates by alumina powder and titania powder, usually use the little alumina powder of particle diameter, but when using average grain diameter to be the alumina powder of 2～8 μ m, can suppress the contraction in when calcining less, the residue pore easily obtains having the required porosity, the porous body of average pore diameter, pore distribution bias and venting quality.The average grain diameter of alumina powder most preferably is 2～6 μ m.And then, preferably comprise the alumina powder of powder 5～30 quality % that powder 50 quality % are above, particle diameter 20 μ m are above of particle diameter 2～20 μ m.Need to prove, the average grain diameter of powder is the value of utilizing laser diffractometry to measure.
The average grain diameter of titania powder is preferably 0.05～3 μ m.When above-mentioned average grain diameter less than 0.05 μ m, need many water during raw materials, easily crack when dry.When above-mentioned average grain diameter surpasses 3 μ m, aluminium titanates synthetic insufficient.The average grain diameter of titania powder is 0.1～2 μ m more preferably.The preferred purity of titania powder is more than 98%.The crystal type of titania powder can be any in Detitanium-ore-type or rutile-type.
The average grain diameter of preferential oxidation aluminium powder is greater than the average grain diameter of titania powder.When using the little titania powder of particle diameter with respect to the large alumina powder of particle diameter, can obtain the loose structure of high porosity, contraction during calcining diminishes, therefore even calcine that for example external diameter 150mm is above, in the situation of the large, honeycomb shape structure of total length 150mm left and right, also can prevent from calcining crackle.
By the Na that will contain in alumina powder
2O is set as 0.05～0.5 quality % and with the Na that contains in titania powder
2O is set as below 0.5 quality %, the further eutectic of formed liquid phase in calcination process is revealed, therefore due to fine glassy phase combining aluminium titanate primary crystallization after calcining, effective effect is played in microscopic checks miniaturization, little thermal coefficient of expansion and the improvement of intensity.The Na that contains in alumina powder
2O is preferably 0.1～0.3 quality %, the Na that contains in titania powder
2Preferred 0.01～0.3 quality % of O.
Add SiO 2 powder 1～6 mass parts by total quality 100 mass parts with respect to above-mentioned titania powder and above-mentioned alumina powder, can make the SiO in the aluminium titanates primary crystallization
2Solid solution capacity is 0.1～1.5%, and can make in the section of the partition after calcining above-mentioned glassy phase with respect to the area ratio of the total area of the primary crystallization of aluminium titanates and glassy phase be 2～12% and/or glassy phase be more than 1 quality % and less than 10 quality % with respect to the mass fraction of the total of the primary crystallization of aluminium titanates and glassy phase.The above-mentioned addition of SiO 2 powder is 2～4 mass parts more preferably.
The average grain diameter of SiO 2 powder is preferably 0.1～30 μ m.When above-mentioned average grain diameter surpasses 30 μ m, because the fusing speed of silica is slack-off, be difficult to generate liquid phase when therefore calcining, be difficult to promote the miniaturization of microscopic checks.In addition, in extrusion molding, when the narrow mould slit that makes plasticity base soil by for example 0.3mm left and right, SiO 2 powder stops up, and the partition of ceramic honeycomb structure cracks as a result.When above-mentioned average grain diameter less than 0.1 μ m, because specific area becomes large, so need many water during raw materials, self supportive of formed body descends, or drying time, wall chapped.The average grain diameter of SiO 2 powder is 1～25 μ m more preferably.In addition, as SiO 2 powder, can use the amorphous silicas such as quartz, fused silica, colloidal silica, the amorphous silica that the at high temperature complete melting of high-purity silica is formed.As long as be noncrystalline, the amorphous silica powder can also can be ball-type for crush type.The purity of SiO 2 powder is preferred more than 99%, further preferred more than 99.5%.Can not make the SiO in the aluminium titanates primary crystallization during due to the silicon-containing compound that uses the mineral such as feldspar
2Solid solution capacity or glassy phase consist of within the scope of the invention, so the present invention uses SiO 2 powder.
By add the magnesium oxide source powder below 0.5～5 mass parts average grain diameter 5 μ m with respect to total quality 100 mass parts of titania powder and alumina powder, can make MgO solid solution capacity in the aluminium titanates primary crystallization is 0.2～5 quality % and to make the MgO amount that contains in glassy phase be 1～20 quality %, when heat endurance improvement, the thermal coefficient of expansion of 800～1250 ℃ of honeycomb molded body diminished as previously mentioned, the intensity of honeycomb molded body increased.In the situation that the average grain diameter of magnesium oxide source powder surpasses 5 μ m, descend with the reactivity of SiO 2 powder, contained MgO quantity not sufficient 1% in glassy phase, the eutectic of glassy phase is revealed and can not be realized.Therefore, can not realize the little coefficient of expansion and high strength.The average grain diameter of magnesium oxide source powder is preferably 0.2～4 μ m, 0.2～2 μ m more preferably.The addition of magnesium oxide source powder is 0.5～2 mass parts more preferably.As the magnesium oxide source powder, can use magnesia, magnesium hydroxide, magnesium carbonate, talcum, spinelle etc., but from easily generated the viewpoint consideration of liquid phase, preferential oxidation magnesium by alumina powder, titania powder and SiO 2 powder calcination process.
(2) calcination condition
During the formed body of calcining alveolate texture, heat up in the temperature range of 1300 ℃～1350 ℃ with the average speed of 10～100 ℃/hr.Usually in the situation of burning ceramics goods, particularly in the situation that the large-sized honeycomb molded body more than its external diameter 150mm, more than total length 150mm, the inhomogeneity viewpoint of the temperature from keep calcination process considers, programming rate is preferably slower.But in the method for the invention, as reaching the calcination condition of the large-sized honeycomb molded body more than total length 150mm more than external diameter 150mm, by with the such ratio of 10～100 ℃/hr faster speed heat up the temperature range of 1300～1350 ℃, can make the further miniaturization of microscopic checks.Its reason is also indefinite, but can think: owing to existing mainly by SiO 2 powder at this temperature field and being defined in the formed liquid phase of magnesium oxide source powder below average grain diameter 5 μ m, and by alumina powder and the synthetic solid solution of titania powder, MgO and SiO are arranged
2The aluminium titanates crystallization, therefore fine glassy phase combining aluminium titanate primary crystallization after the calcining, have the effect that makes the microscopic checks miniaturization.Above-mentioned average heating speed more preferably 30～80 ℃/hr, most preferably be 50～80 ℃/hr.Also can heat up with 10～100 ℃/hr in than the wider temperature range of the scope of 1300～1350 ℃, but its scope should be limited in 1250～1400 ℃, the programming rate of other temperature range should not produce the scope of calcining crackle at honeycomb molded body suitably to be determined, but should adopt the programming rate lower than the programming rate in said temperature scope.
Calcining is implemented under 1400～1650 ℃.If the temperature that less than is 1400 ℃, synthetic insufficient due to the aluminium titanates that utilizes alumina powder and titania powder, so thermal coefficient of expansion becomes large.When surpassing 1650 ℃, in the situation that add pore-creating material described later, densified enhancing and the porosity diminishes, it is large that the pressure loss of partition becomes.In addition to be sintered into this aspect also unfavorable.The preferred scope of calcining heat is 1500～1600 ℃.
Retention time under 1400～1650 ℃ of the maximum temperatures in when calcining was preferably more than 24 hours.Be more than 24 hours by making the maximum temperature retention time, fine pore disappears, thereby under the effect of pore-creating material described later, it is large that average pore diameter becomes.Its result can increase venting quality, obtains the low pressure loss performance.
(3) pore-creating material
Preferably add the pore-creating material in the material that mixed oxidization aluminium powder, titania powder, SiO 2 powder and magnesium oxide source powder form.By adding the pore-creating material, can obtain the required porosity, average pore diameter and venting quality.as the pore-creating material, can be used alone or in combination two or more known wheat flours, graphite, starch, cellulose, hollow ceramic (ceramic balloon), polyethylene, polystyrene, polypropylene, nylon (registration mark), polyester, acrylic acid, phenol, epoxides, ethylene-vinyl acetate copolymer, styrene-butadiene block copolymer, styrene-isoprene block copolymer, polymethyl methacrylate, Methyl Methacrylate-acrylonitrile Copolymer, the ammonia ester, wax etc., the Foamex that is wherein particularly preferably formed by Methyl Methacrylate-acrylonitrile Copolymer.
Utilize the following examples further to describe the present invention in detail, but the present invention is not limited to these examples.
Embodiment 1
The rutile titania powder A of table 1 and alumina powder D mol ratio (counting in mass ratio 43.9: the 56.1) weighing (with reference to table 2) by 50: 50 will be shown in, mix Foamex after the development bubble that comprises iso-butane of magnesium oxide powder C (with reference to table 1), 14 mass parts of amorphous silica powders A (with reference to table 1), 1.0 mass parts of 3 mass parts and the methylcellulose of 6 mass parts with respect to total 100 mass parts of these powder, add entry and carry out mixingly, make plasticity base soil.This plasticity base soil extrusion molding is obtained the formed body of alveolate texture.This formed body is dry, use gas burner to be heated to 1000 ℃ with 150 hours from room temperature in atmosphere, speed from 1000 ℃ to 1300 ℃ with 10 ℃/hr heats up, heat up from 1300 ℃ to the 1350 ℃ speed with 32 ℃/hr, heat up from 1350 ℃ to the 1600 ℃ speed with 10 ℃/hr, by keeping 5 hours under 1600 ℃, calcine, obtain the honeycomb molded body take aluminium titanates as primary crystallization with external diameter 152mm, length 152mm, a wall thickness 0.25mm and partition spacing 1.4mm.
Cut test film by this honeycomb molded body, to the crystalline phase that consists of honeycomb molded body, the SiO in the aluminium titanates primary crystallization
2And the porosity, average pore diameter, pore distribution bias σ, venting quality, A axial compression contracting intensity, the thermal coefficient of expansion (CTE) of composition, average-size, area ratio, mass fraction and the partition of the solid solution capacity of MgO, glassy phase, estimate the heat endurance of 1100 ℃.
The crystalline phase that consists of honeycomb molded body utilizes the RINT1500 processed of Rigaku Co., Ltd. Neo-Confucianism of company (X-ray diffraction device) to measure the further X-ray diffractogram of pulverizing the Powdered sample that forms of above-mentioned test film, identifies and obtains as the basis take the data of JCPDS data file.The ratio of crystalline phase is by (230) face diffracted intensity (I of aluminium titanates
AT (230)), Al
2O
3(104) face diffracted intensity (I of corundum
Corundum (104)), TiO
2(110) face diffracted intensity (I of rutile
Rutile (110)) and (311) face diffracted intensity (I of spinelle
Spinelle (311)) strength ratio calculate.
SiO in the aluminium titanates primary crystallization
2And the solid solution capacity of MgO utilizes EPMA (EPMA-1610 processed of Shimadzu Seisakusho Ltd.) that the section that the partition that will be embedded in the honeycomb molded body after the calcining in resin has ground is analyzed, and obtained as the basis take the calibration curve of making in advance by the X ray intensity of the Si in the aluminium titanates primary crystallization of gained and Mg.
The composition of glassy phase, average-size and area ratio utilize FE-SEM (can the community day vertical System of strain formula makes the System S-4000 of institute) that the section that the partition that will be embedded in the honeycomb molded body after the calcining in resin has ground is observed and obtained.The composition of glassy phase utilizes the EDX analytical equipment to measure, and the average-size of glassy phase and area ratio (the glassy phase area is with respect to the ratio of the total area of aluminium titanates crystallization and glassy phase) utilize image analysis software (the Image-Pro Plus processed of Media Cybemetics company) to be calculated by the SEM photo of partition section.Glassy phase is present in the gap of crystalline phase and the crystalline phase of aluminium titanates, with the size of its maximum length as glassy phase.The average-size of glassy phase draws with its mean value calculation by measuring the size of 20 place's glassy phases.
The mass fraction a (quality %) of glassy phase is by the SiO in the aluminium titanates primary crystallization of obtaining as previously mentioned
2SiO in solid solution capacity b (quality %), glassy phase
2The SiO of amount c (quality %) and raw material
2Mix proportions d (quality %) formula: a=100 * (d-b)/(c-b) calculate.
The porosity of the partition of honeycomb molded body, average pore diameter, pore distribution bias σ [=log (D20)-log (D80)] utilize mercury penetration method to measure.(10mm * 10mm * 10mm) be arranged in the determination unit of the Micromeritics Auto PoreIII processed of company after decompression in the unit, imports mercury and pressurizes the test film that will be cut by honeycomb molded body.By the pressure in when pressurization be pressed into relation between the volume of the mercury in the pore that is present in test film, obtain the relation between pore diameter and accumulation pore volume.The pressure setting that imports mercury is 0.5psi (0.35 * 10
-3Kgf/mm
2), the constant during by the calculation of pressure pore diameter is set as contact angle=130 °, and surface tension is 484dyne/cm.
The venting quality of the partition of honeycomb molded body cuts out partition from the honeycomb molded body after calcining, make the discoid test film of external diameter 20mm, use Perm-Porometer (Porous Materials CFP-1100 processed) to measure with known method.
The specification M505-87 that A axial compression contracting intensity can be formulated according to civic organization's automotive engineering " exhausted gases purification with the test method of ceramic integral carrier " measures.
Thermal coefficient of expansion (CTE) according to the direction that makes total length and path direction almost consistent mode cut out the test film of the size of section shape 4.8mm * 4.8mm * total length 50mm, use thermo-mechanical analysis device (TMA, the Thermo Plus processed of Co., Ltd. Neo-Confucianism of Rigaku company, compression load mode/differential expansion fashion) limit applies firm demand 20g limit and measures recruitment with the length of the total length direction of 10 ℃/min. of programming rate when being heated to 800 ℃ for 35 ℃, obtain as the mean thermal expansion coefficients between 35～800 ℃.
The surplus ratio of the aluminium titanates when the stability of 1100 ℃ are carried out heat treatment in 100 hours with the test film with 10mm * 10mm * 10mm in the electric furnace of the air atmosphere of 1100 ℃ is estimated.The surplus ratio of aluminium titanates (X) is by the X-ray diffraction intensity of the test film before and after the above-mentioned heat treatment of mensuration, by (230) face diffracted intensity (I of aluminium titanates
AT (230)) and TiO
2(110) face diffracted intensity (I
TiO2 (110)) obtain the ratio R[I of aluminium titanates
AT (230)/ (I
TiO2 (110)+ I
AT (230))], utilize formula: X={ (heat treatment before and after R)/(R before heat treatment) } * 100 (%) try to achieve.
For the honeycomb molded body of embodiment 1, be aluminium titanates by the results verification primary crystallization of X-ray diffraction, comprise corundum seldom.And then by the results verification that EPMA analyzes and SEM observes, in the aluminium titanates of primary crystallization, solid solution has SiO
2And MgO, when having this aluminium titanates primary crystallization, have the MgO of comprising and SiO
2Glassy phase.With SiO
2And the porosity, average pore diameter, pore distribution bias σ, venting quality, A axial compression contracting intensity, the thermal coefficient of expansion of composition, average-size, area ratio, mass fraction and the partition of the solid solution capacity of MgO in primary crystallization, glassy phase, be shown in table 3 the heat endurances of 1100 ℃.
The kind of the powder that change as shown in table 2 is used, raw material fusion be calcination condition when, in addition, and operation similarly to Example 1, the ceramic structure of making embodiment 2～14 and comparative example 1～6.Particularly, carry out change described as follows.
The honeycomb molded body of embodiment 2 uses magnesium hydroxide as the magnesium oxide source powder, and changes the addition of Foamex, makes with the same operation of the honeycomb molded body of embodiment 1 in addition.
The honeycomb molded body of embodiment 3 changes calcining heat, and operation is made similarly to Example 1 in addition.
The honeycomb molded body of embodiment 4 changes powder, the addition of Foamex, programming rate, the highest maintenance temperature when calcining of silica, makes with the same operation of the honeycomb molded body of embodiment 1 in addition.
The mass ratio (being calculated in molar ratio as 49: 51) that the honeycomb molded body of embodiment 5 is set as 42.9: 57.1 with the mix proportions of rutile titania powder A and alumina powder D, and the programming rate when changing the addition of kind, magnesium oxide powder of SiO 2 powder and calcining, make with the same operation of the honeycomb molded body of embodiment 1 in addition.
The honeycomb molded body of embodiment 6 changes the addition of magnesium oxide powder, makes with the same operation of the honeycomb molded body of embodiment 1 in addition.
The honeycomb molded body of embodiment 7 changes kind and addition and the calcining heat of magnesium oxide powder, makes with the same operation of the honeycomb molded body of embodiment 1 in addition.
The honeycomb molded body of embodiment 8 changes the addition of magnesium oxide powder, makes with the same operation of the honeycomb molded body of embodiment 1 in addition.
The honeycomb molded body of embodiment 9 changes addition and the calcining heat of magnesium oxide powder, makes with the same operation of the honeycomb molded body of embodiment 1 in addition.
The honeycomb molded body of embodiment 10 changes kind, calcining heat and the time of alumina powder, makes with the same operation of the honeycomb molded body of embodiment 1 in addition.
The honeycomb molded body of embodiment 11 changes the kind of alumina powder, kind, calcining heat and the time of SiO 2 powder, makes with the same operation of the honeycomb molded body of embodiment 1 in addition.
The honeycomb molded body of embodiment 12 uses rutile titania powder A and alumina powder C, the mass ratio (being calculated in molar ratio as 51: 49) that its mix proportions is set as 44.9: 55.1, change addition, the kind of magnesium oxide powder, programming rate, calcining heat and the time when calcining of SiO 2 powder, make with the same operation of the honeycomb molded body of embodiment 1 in addition.
The programming rate when honeycomb molded body of embodiment 13 changes the addition of kind, SiO 2 powder of titania powder and calcining is made with the same operation of the honeycomb molded body of embodiment 12 in addition.
The programming rate when addition of the honeycomb molded body change SiO 2 powder of embodiment 14 and calcining is made with the same operation of the honeycomb molded body of embodiment 13 in addition.
Comparative example 1 and 2 honeycomb molded body use rutile titania powder A and alumina powder C, the mass ratio (being calculated in molar ratio as 51: 49) that its mix proportions is set as 44.9: 55.1, change the addition of SiO 2 powder, kind and calcining heat and the time of magnesium oxide powder, operation is made similarly to Example 1 in addition.
The honeycomb molded body of comparative example 3 changes kind, programming rate and calcining heat and the time when calcining of magnesium oxide powder, makes with the same operation of the honeycomb molded body of embodiment 1 in addition.
The honeycomb molded body of comparative example 4 uses rutile titania powder A and alumina powder E, the mass ratio (being calculated in molar ratio as 47: 53) that its mix proportions is set as 41: 59, addition and calcining heat and the time of the kind of change magnesium oxide powder and addition, Foamex, operation is made similarly to Example 1 in addition.
The honeycomb molded body change titania powder of comparative example 5 and the kind of alumina powder, kind and addition and calcining heat and the time of magnesium oxide powder, make with the same operation of the honeycomb molded body of comparative example 4 in addition.
The honeycomb molded body of comparative example 6 is made with the same operation of the honeycomb molded body of embodiment 1 except not adding magnesium oxide powder.
For the honeycomb molded body of resulting embodiment 2～14 and comparative example 1～6, the crystalline phase that consists of honeycomb molded body, the SiO in the aluminium titanates primary crystallization are estimated in operation similarly to Example 1
2And the porosity, average pore diameter, pore distribution bias σ, venting quality, A axial compression contracting intensity, the thermal coefficient of expansion (CTE) of composition, average-size, area ratio, mass fraction and the partition of the solid solution capacity of MgO, glassy phase reach the heat endurance at 1100 ℃.
For the honeycomb molded body of embodiment 2～14 and comparative example 1～6, confirm similarly to Example 1 to have with solid solution SiO is arranged
2The aluminium titanates that reaches MgO is primary crystallization, has the MgO of comprising and SiO
2Glassy phase.
[table 1]
Annotate (1): aluminium oxide A comprises the particle of 5 quality % 2～10 μ m.
Annotate (2): aluminium oxide B comprises the particle of 12 quality % 2～10 μ m.
Annotate (3): aluminium oxide C comprises particle, the above particle of 2 quality %20 μ m of 54 quality % 2～10 μ m.
Annotate (4): aluminium oxide D comprises particle, the above particle of 7 quality %20 μ m of 66 quality % 2～10 μ m.
Annotate (5): aluminium oxide E comprises particle, the above particle of 20 quality %20 μ m of 40 quality % 2～10 μ m.
[table 2]
Table 2 (continuing)
Table 2 (continuing)
[table 3]
Table 3 (continuing)
Table 3 (continuing)
Table 3 (continuing)
Table 3 (continuing)
Annotate (1): the surplus ratio (%) of the aluminium titanates after keeping 100 hours under 1100 ℃ of atmosphere.
As shown in table 1～3, the mix proportions of titania powder and alumina powder is by mol the scope of 47: 53～53: 47, total quality with respect to them is added SiO 2 powder 1～6 mass parts and magnesium oxide powder 0.5～5 mass parts below average grain diameter 5 μ m, the programming rates of 1300～1350 ℃ be 10 ℃/more than hr and calcining heat be the honeycomb molded body of the embodiments of the invention 1～14 made under 1450～1650 ℃ of such conditions, can confirm that solid solution has SiO
2And the primary crystallization of the aluminium titanates of MgO and comprise MgO and SiO
2Glassy phase, this glassy phase area ratio is 2～8%, contained MgO amount is 2.5～15%.These honeycomb molded body porositys are 40～70%, and average pore diameter is 10～40 μ m, and the pore distribution bias is below 0.4, and the venting quality of partition is 1.2 * 10
-12m
2Above, A axial compression contracting intensity is more than 3.8MPa, and the thermal coefficient of expansion of partition is 12 * 10
-7/ ℃ below, the surplus ratio of the aluminium titanates crystallizations when keeping 100 hours for 1100 ℃ is more than 95%, have both low pressure loss is arranged, high strength, high resistance to sudden heating, the heat endurances of 1100 ℃.
On the other hand, less than for the honeycomb molded body of 1% comparative example 1, because the area occupation ratio of glassy phase is little, the glass phasor is few, so A axial compression contracting intensity is little for the adding proportion of silica, and thermal coefficient of expansion is large.Greater than for the honeycomb molded body of 6% comparative example 2, because the area ratio of glassy phase is large, the glass phasor is many, so A axial compression contracting intensity is little for the adding proportion of silica, and thermal coefficient of expansion is large.For the honeycomb molded body of the comparative example 3 of calcining heat over 1650 ℃, it is large that the average-size of glassy phase becomes, and A axial compression contracting intensity is little, and thermal coefficient of expansion is large.For magnesian average grain diameter greater than 2 μ m, magnesian addition less than 0.5%, the average grain diameter of aluminium oxide is greater than for the honeycomb molded body of the comparative example 4 of 10 μ m, the MgO quantity not sufficient 2.5% of glassy phase, A axial compression contracting intensity is little, thermal coefficient of expansion is large.Greater than for the honeycomb molded body of 5% comparative example 5, the MgO amount of glassy phase surpasses 15% for magnesian adding proportion, and the venting quality of partition is little, and thermal coefficient of expansion is large.For not adding the honeycomb molded body of magnesian comparative example 6, because the microscopic checks number is few, so A axial compression contracting intensity is little, and thermal coefficient of expansion is large.And then owing to there is no solid solution MgO in the aluminium titanates primary crystallization, so heat endurance is obviously low.
Embodiment 15
By solid solution, MgO and SiO are arranged to what make in embodiment 1
2The aluminium titanates primary crystallization and the honeycomb molded body that consists of of glassy phase (shape with external diameter 152mm, length 152mm, a wall thickness 0.25mm and partition spacing 1.4mm has the porosity 45.2%, average pore diameter 23.5 μ m, pore distribution bias 0.24 and venting quality 2.4 * 10
-12m
2Characteristic) path after alternately sealing makes its both ends become tartan with known method, is removed the peripheral part of this honeycomb molded body by processing, making external diameter is Φ 141mm.Outside wall portions is set filling coating material (colloidal silica that is scaled 5 mass parts by solid constituent is contained in 100 Quality Mgmt Dept with respect to the aluminium titanates powder) and carry out drying by the formed groove that extends vertically of the partition that is positioned at its outer peripheral face, makes external diameter Φ 144mm, length 152mm, a wall thickness 0.25mm, and the honeycomb filter of the structure that is shown in Fig. 1 (a) and Fig. 1 (b) of partition spacing 1.4mm.
Comparative example 7
Use the cordierite raw material, make the practical cordierite honeycomb filter of the structure that is shown in Fig. 1 (a) and Fig. 1 (b) of known method.The external diameter of this honeycomb filter is that 152mm, length are that 152mm, a wall thickness are that 0.3mm, partition spacing are 1.57mm, has the porosity 63%, average pore diameter 22 μ m, pore distribution bias 0.7, venting quality 3.2 * 10-12
-12m
2Characteristic.
Be determined at the pressure loss characteristic of the ceramic honeycomb filter of gained in embodiment 15 and comparative example 7.Pressure loss characteristic by in the ceramic honeycomb filter on being fixed in pressure loss testing stand with 4Nm
3The pressure loss before and after the filter of/min flow during by air is estimated.Its result, the pressure loss of the honeycomb filter of embodiment 15 are 100mmAq, and the pressure loss of the honeycomb filter of comparative example 7 is 90mmAq.The honeycomb filter of confirming the embodiment 15 that use aluminum-titanate-based ceramic honeycomb structure of the present invention is made can obtain the low pressure loss performance equal with practical cordierite honeycomb filter.
Claims (13)
1. aluminum-titanate-based ceramic honeycomb structure, it has a plurality of paths that the partition with porous separates, and it is characterized in that, and described partition has the MgO of 0.2～5 quality % and the SiO of 0.1～1.5 quality % by solid solution at least
2The primary crystallization of aluminium titanates and glassy phase consist of, described glassy phase contains the SiO of 40～80 quality %
2And the MgO of 1～20 quality %, the average-size of the glassy phase in the section of described partition is below 30 μ m, and the described glassy phase in the section of described partition is 2～12% with respect to the area ratio of the total area of the primary crystallization of described aluminium titanates and described glassy phase.
2. aluminum-titanate-based ceramic honeycomb structure, it has a plurality of paths that the partition with porous separates, and it is characterized in that, and described partition has the MgO of 0.2～5 quality % and the SiO of 0.1～1.5 quality % by solid solution at least
2The primary crystallization of aluminium titanates and glassy phase consist of, described glassy phase contains the SiO of 40～80 quality %
2And the MgO of 1～20 quality %, the average-size of the glassy phase in the section of described partition is below 30 μ m, described glassy phase is more than 1 quality % and less than 10 quality % with respect to the mass fraction of the total of the primary crystallization of described aluminium titanates and described glassy phase.
3. aluminum-titanate-based ceramic honeycomb structure as claimed in claim 1 or 2, it is characterized in that, the porosity of described partition is 40～70%, average pore diameter is 10～40 μ m, pore distribution bias σ is below 0.4, wherein, σ=log (D20)-log (D80), D20 is the pore diameter when being illustrated in 20% the pore volume that is equivalent to whole pore volume in expression pore diameter and the curve of accumulating the relation between pore volume, unit is μ m, pore diameter when D80 is illustrated in 80% the pore volume that is equivalent to whole pore volume equally, unit is μ m, D80＜D20 wherein, described accumulation pore volume is the value of having accumulated from the pore diameter of maximum to the pore volume specific pore diameter.
4. aluminum-titanate-based ceramic honeycomb structure as claimed in claim 1 or 2, is characterized in that, the venting quality of described partition is 2 * 10
-12m
2Above.
5. aluminum-titanate-based ceramic honeycomb structure as claimed in claim 1 or 2, is characterized in that, the A axial compression contracting intensity of described honeycomb molded body is more than 4MPa.
6. aluminum-titanate-based ceramic honeycomb structure as claimed in claim 1 or 2, is characterized in that, the thermal coefficient of expansion of described partition is 12 * 10
-7/ ℃ below.
7. aluminum-titanate-based ceramic honeycomb structure as claimed in claim 1 or 2, is characterized in that, when described partition was kept 100 hours in the atmosphere of 1100 ℃, the surplus ratio of aluminium titanates was more than 95%.
8. the manufacture method of an aluminum-titanate-based ceramic honeycomb structure, is characterized in that, will contain 0.05～0.5 quality %Na with respect to 100 mass parts
2The alumina powder of O with contain the 0.5 following Na of quality %
2The total amount of the powder in the titania powder of O is adjusted to take molar ratio computing as the scope of 47: 53～53: 47, at least mix the SiO 2 powder of 1～6 mass parts and the following magnesium oxide source powder of average grain diameter 5 μ m of 0.5～5 mass parts, after making the formed body of alveolate texture by this material that mixes, average speed with 10～100 ℃/hr heats up in the temperature range of 1300 ℃ to 1350 ℃ again, and calcine at the highest maintenance temperature of 1400～1650 ℃, obtain thus by solid solution, MgO and SiO being arranged at least
2The primary crystallization of aluminium titanates and the aluminum-titanate-based ceramic honeycomb structure that consists of of glassy phase.
9. the manufacture method of aluminum-titanate-based ceramic honeycomb structure as claimed in claim 8, it is characterized in that, the average grain diameter of described alumina powder is 0.1～10 μ m, the average grain diameter of described titania powder is 0.05～3 μ m, and the average grain diameter of described SiO 2 powder is 0.1～30 μ m.
10. the manufacture method of aluminum-titanate-based ceramic honeycomb structure as claimed in claim 8 or 9, is characterized in that, the average grain diameter of described alumina powder is 2～6 μ m.
11. the manufacture method of aluminum-titanate-based ceramic honeycomb structure, is characterized in that as claimed in claim 8 or 9, adds the pore-creating material in described composite material.
12. the manufacture method of aluminum-titanate-based ceramic honeycomb structure, is characterized in that as claimed in claim 8 or 9, keeps more than 24 hours at the highest described maintenance temperature.
13. the material powder for the manufacture of aluminum-titanate-based ceramic honeycomb structure is for the manufacture of by solid solution, MgO and SiO being arranged at least
2The primary crystallization of aluminium titanates and the aluminum-titanate-based ceramic honeycomb structure that consists of of glassy phase, it is characterized in that, be will contain 0.05～0.5 quality %Na with respect to 100 mass parts
2The alumina powder of O and contain the 0.5 following Na of quality %
2The total amount of the powder in the titania powder of O is adjusted to take molar ratio computing as 47: 53～53: 47 scopes has mixed at least that the following magnesium oxide source powder of average grain diameter 5 μ m of the SiO 2 powder of 1～6 mass parts and 0.5～5 mass parts forms.
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| PCT/JP2008/070821 WO2009063997A1 (en) | 2007-11-14 | 2008-11-14 | Aluminum titanate based ceramic honeycomb structure, process for production of the same and raw material powder for the production thereof |
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| CN101861288A (en) | 2010-10-13 |
| US8663777B2 (en) | 2014-03-04 |
| JP5544882B2 (en) | 2014-07-09 |
| EP2221287A4 (en) | 2011-12-07 |
| WO2009063997A1 (en) | 2009-05-22 |
| EP2221287B1 (en) | 2015-06-03 |
| US20100310819A1 (en) | 2010-12-09 |
| PL2221287T3 (en) | 2015-12-31 |
| US9011757B2 (en) | 2015-04-21 |
| US20130214463A1 (en) | 2013-08-22 |
| JPWO2009063997A1 (en) | 2011-03-31 |
| EP2221287A1 (en) | 2010-08-25 |
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